Halo-aliphatic esters of 2-chloroallyl alcohol



HALO-ALIPHATIG ESTERS OF 2-CHLORO- PATENT OFFICE,

ALLYL ALCOHOL Fred Lowell Taylor, Midland, Mich., assignor to The Dow Chemical Company, Midland, Mich., a corporation of Michigan No Drawing. Application July 1' 7, 1939, Serial N: 284,921

9 Claims.

This invention concerns a new class of chemical compounds, namely the. esters of 2-chloroallyl alcohol and halogenated carboxylic acids of the aliphatic series. Such esters may be more sented bythe general formula 01 oH@= ;cH,-o-c-R wherein R represents a halogenated alkyl radical, 0 i. .e., an alkyl radical containing one or more halogen substituents. Examples of such esters are 2-chloroallyl chloroacetate, 2-chloroallyl alpha, beta-dibromopropionate, '2-chloroallyl alpha- .chlorolaurate; Z-chloroallyl beta-bromocaproate,

'2-chloroallyl gamma-bromobutyrate, 2-chloroallyl alphachloroisobutyrate, 2-chloroallyl alpha, alpha-dichloroisovalerate, 2-chloroallyl trichloroacetate, 2-chloroallyl alpha-bromostearate, 2-

chloroallyl gamma-bromocaprylate, etc. All such 2'0 esters are useful as modifying agents in the polymerization of vinyl compounds and vin'ylidene halides, and as intermediates in the preparationof other,organic chemicals The new esters having the above generalfor- 25 mula may be prepared loy reacting 2-chloroal1yl alcohol with-a halogenated aliphatic acid or its anhydride. ,The reaction is preferably carried out by heating amixture of 2-chloroallyl alcohol and the, desired acid orfacid anhydride to a tempera- 0' tprel o'f approximately 9 0 -l50 C,

a all proportion, e. i g.,- 0.01-0.04 molecular equivalent, of an esterification catalyst,;such as sulphuric acid, benzene sulfonicacid, 'etc., may be employed. When 2-chloroallyl alcohol is reacted 55' with a halogenated aliphatic acid,'water is formed aurm'gthere cm n, and, if desired, a.waterimmiscible organic liquid, such asbenzene, toluene, me hylene. chloride, etc'., may be added to the reaction mixture forthe purpose of promot- 6 ing distillation and removal of the water. The reaction is usually complete in from 3 to hours, after which the mixture is neutralized, washed with water, and dried, and the ester product is separated'andpurifie'd by fractional distillation. An alternative method for the preparation of the:;new-: esters comprises reacting 2-chloroallyl alcohol withla halogenated aliphatic acid halide, such as chloroacetyl chloride, alpha-chloropropionyl bromide, etc. The reaction is preferably carried out by gradually adding the acid halide to the alcohol while heating the mixture to a reaction temperature of approximately 30-l20. C :Up on completion of the reaction, the mixture is neutralized, washed with water, and the ester 5 nr uctl sesspar te a .herei be r d d- If desired,

The following examples illustrate a number of ways in which theprinciple of the invention has been applied, but are not to be construed as limiting the same: Example 1 A mixture of 92.5 grams (1.0 mole) of z-chloro- 'allyl-alcoholand 100 grams -(1.06 moles) of chloroacetic acid was heated at a temperature of approximately 85 C. forhours in aflask fitted with'a dropping funnel; condenserfand' receiver arranged in such a manner as to permit distillation of water from the mixture. During the pletion of the reaction, the methylene chloride was distilled offand the crude ester product was cium chloride. The product was then fractionally uid distilling at approximately 75'77 C. under 5 millimeters pressure and having a specific gravity of about 1.307? at /25" C. and an index of refraction, 1

n 1.4691 2-chloroallyl chloroacetate was also prepared by warming a mixture of 92.5 grams (1.0 mole),

of ,2-chloroallyl alcohol and 175 grams (1.0. mole) of chloroacetic anhydride on a steam bath for about hour and thereafter purifying and separating the ester product as described above.

Example 2 v 2-chloroallyl chloroacetate was prepared from chloroacetyl chloride in the following manner;

1450 grams of chloroacetyl chloride was added gradually with stirring to 983 grams of technical Z-chloroallyl alcohol while maintaining a reaction temperature of approximately -35 C. When all of the chloroacetyl chloride had been added,

the temperature was gradually raised to 95C.

over a period of three hours, after which time the mixture was cooled, washed with water and aqueous sodium bicarbonate, and dried over anhydrous potassium carbonate. The z-chloroallyl chlo-ropropionic acid was heated at approximately 90-160 C. for 1 hours. The excess alcohol heating, methylene chloride wasv added drop;wise 'tdfacilitate the distillationof water. "Upon can:

neutralized with aqueous sodium bicarbonata washed with water, and dried over anhydrous caldistilled under vacuum. wherebyyz-chloroallyl" chloroacetate was obtained as a water-White liq:

was then distilled off and the crude ester product was neutralized with aqueous sodium bicarbonate, washed with water, dried over anhydrous potassium carbonate, and fractionally distilled under vacuum. There was obtained 2-chloroallyl alpha-chloropropionate, a colorless liquid distilling at approximately 72-74 C. under 5 millimeters pressure and having a specific gravity of about 1.243 at 25/25 C. and an index of refraction,

Example 4 25.4 grams (0.2 mole) of beta-chloropropionyl chloride was added gradually with stirring to 20.0 grams (0.22 mole) of 2-chloroallyl alcohol (1.0 mole) of 2-chloroa1lyl alcohol was heated at approximately 150 C. for 1 hours. Excess alcohol was distilled from the reaction mixture and the latter was washed, neutralized, dried, and fractionally distilled as in Example 3. There was obtained 2-chloroallyl alpha-chloro-alphamethyl-butyrate, a colorless liquid distilling at approximately 80-82 C. under 4 millimeters pressure, and having a specific gravity of about 1.162 at 25/25 C. and an index of refraction,

The following table describes several other 2- chloroallyl esters of the present class, each of which was prepared by a procedure similar to that described above.

while maintaining a reaction temperature of ap- Table Compound Formula Bolling point g v ifig t Riggggve Mm 25/25 o. 11?;

Cl 0 C1 CH3 Z-chloroallylalpha-chloroiscvalerate CHZ=( J CHI O'( JCHHCHQ 87-88 4 1.159 1.4592

01 0 Cl 2-chloroally1alpha-chloro-n-butyrate CH1=( JOHa0 H-CHz-OH3 75-76 3 1.194 1.4598

Cl 0 Cl 2chloroallyl dichloroacetate CH;=( CHzO-(J( 3H 92-96 14 1. 4833 Cl 0 Cl 2-chloroallyl trichloroacetate CHFI-OHr-O--(J-Cl 79-81 5 1. 481 1. 4838 C1 0 Br 2-chloroallyl bromoacetate CHa=CH:O( JC lHz 80-82 5 1. 610 1. 4934 Cl 0 'Br Br 2-chloroa11ylalpha,bet:i-dibromo-n-butyrate... CH2=( 3 GH2O- H )H-'CH3 156-159 28 1.631 1.5113

about 1.254 at 2'5/25" C. and an index of refraction,

Example 5 A mixture of 23.2 grams (0.1 mole) of alpha, beta-di-bromopropionic acid, 50.0 grams (0.54 mole) of 2-chloroallyl alcohol, and 0.2 gram of concentrated sulphuric acid was heated at a temperature of approximately 7580 C. for 1'7 hours while distilling ofi water with methylene chloride as in-Example 1. The methylene chloride was removed by distillation and the ester product was dried over anhydrous potassium carbonate and was purified by fractional distillation under vacuum. 2-chloroallyl alpha,beta-dibromopropionate was obtained as a colorless liquid distilling at approximately 154-157 C. under 30 millimeters pressure and having a specific gravity of about 1.803 at 25/25 C. and an index of refraction,

Example 6 A mixture of 68.2 grams (0.5 mole) of alphachloro-alpha-methyl-butyric acid and 92.5 grams This application is a continuation-in-part of my co-pending application, Serial No. 232,007, filed September 27, 1938.

Other modes of applying the principle of my invention may be employed instead of those explained, change being made as regards the materials employed or the methods disclosed, provided the products stated by any of the following claims or the equivalent of such stated products be obtained.

I therefore particularly point out and distinctly claim as my invention:

1. An ester of 2-chloroa1lyl alcohol and a halogenated carboxylic acid of the aliphatic series.

2. An ester of 2-chloroally1 alcohol and a chlorinated acid of the aliphatic series, said ester having the general formula I ll CH2=OCH2O-CR wherein R represents a chlorinated alkyl radical.

3. An ester of 2-chloroal1yl alcohol and a brominated carboxylic acid of the aliphatic series, said ester having the general formula wherein R" represents a brominated alkyl radical.

4. An ester of 2-chloroallyl alcohol and an alpha-halo-aliphatic acid, said ester having the general formula wherein Y represents a substituent selected from the group consisting of hydrogen and chlorine, and Z represents a substituent selected from the group consisting of alkyl radicals and hydrogen.

6. An ester of 2-chloroa1lyl alcohol and an alpha-chloro-aliphatic acid, said ester having the general formula 01 ll c1 wherein Z represents a substituent selected from the group consisting of alkyl radicals and hydrogen.

7. 2-ch1oroallyl chloroacetate, a colorless liquid distilling at approximately 75-'77 C. under 5 millimeters pressure and having a specific gravity of about 1.3077 at 25/25 C. and the formula 8. 2-chloroallyl alpha-chloropropionate, a colorless liquid distilling at approximately '72-74 C.

under 5 millimeters pressure and having a specific gravity of about 1.243 at 25/25 C. and the formula 9. Z-chloroallyl alpha-chloro-n-butyrate, a colorless liquid distilling at approximately 75- 76 C. under 3 millimeters pressure and having a specific gravity of about 1.194 at 25/25 C. and the formula FRED LOWELL TAYLOR.

CERTIFICATE OF CORRECTION. Patent No. 2,221,275. November 12, 191 0.

FRED LOWELL TAYLOR.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows Page 2, first column, line 52, Example 1+, for "n? 1.5229" read --n :1.)+67O; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 21st day of January, A. D. l9L1l.

Henry Van Arsdale, (S al) Acting Commissioner of Patents. 

